KR20200085010A - Cleaning composition for photoresist mixture - Google Patents

Abstract

The present invention relates to a photoresist mixture cleaner composition comprising a compound represented by chemical formula 1 and a compound represented by chemical formula 2. In particular, the photoresist mixture cleaner composition can effectively eliminate photoresist mixtures precipitated inside drainpipes, without causing corrosion therein, even when used in a less amount than that of the photoresist mixtures, and retains excellent cleaning strength even after a long time. In chemical formula 1, R_1 to R_3 are each independently hydrogen, a hydroxy group, a C1-C3 alkyl group, or a C1-C3 alkoxy alkyl group; and R_4 is a C1-C4 linear or branched alkyl group. In chemical formula 2, R_5 is a C1-C4 alkyl group.

Description

Photoresist mixture cleaning solution composition {CLEANING COMPOSITION FOR PHOTORESIST MIXTURE}

The present invention relates to a photoresist mixture cleaning solution composition.

In the manufacturing process of a display device, lithography technology is used to manufacture an electronic circuit or a pixel for realizing color. The lithography process is a method used to create a fine pattern on a substrate, and transfers the circuit pattern of the mask to the substrate by irradiating light through a mask on which a desired pattern is printed on a substrate on which a photosensitive material (also called photoresist) is applied. Process.

In the developing process, the photosensitive material, such as a desired circuit pattern, is obtained by selectively removing a portion of a light-receiving or light-receiving portion from a substrate by selectively interacting with a developer, depending on the type of photoresist in the developing process. .

As described above, as a method of applying the photosensitive material to the substrate, an application device, for example, a nozzle or the like is used. As this process is repeatedly performed, a residue of the photosensitive material remains in the application device and the nozzle is clogged. Will occur.

In order to improve this phenomenon, various solvents are used as a method for cleaning the generated residues, and residues cleaned by the solvents are moved to a wastewater treatment site through a drain. However, in this process, the solvent applied to each nozzle is various, and the mixture of the residue and the solvent dissolved and flowed therefrom is transferred to the wastewater treatment site through the drain, and the mixture is reprecipitated in the drain pipe. When this occurs, a problem occurs in which the defect rate of the device increases.

In this regard, Republic of Korea Patent Publication No. 10-2011-0016137, based on the total weight of the composition, from the group consisting of ethyl-3-ethoxy propionate (EPP) and ethyl-3-methoxy propionate (NMP) 5 to 25% by weight of at least one selected; 5 to 20% by weight of propylene glycol monomethyl ether (PGME); And a thinner composition for removing a photosensitive resin capable of efficiently removing a photosensitive film in a short time by including 60 to 90% by weight of normal butyl acetate (nBA).

In addition, Korean Patent No. 10-1379649 discloses 85 to 96% by weight of propylene glycol monomethyl ether (PGME), 1 to 8% by weight of normal butyl acetate (n-BA) and methyl beta-methoxy propionate (MMP). It has been described for a thinner composition excellent in cleaning power for photoresists by including 1 to 13% by weight.

However, although the above patents can remove the photoresist, there is a problem in that it is difficult to improve the defect rate because the solubility of the mixtures of various compositions reprecipitated in the piping of the drain hole is poor.

Republic of Korea Patent Publication No. 10-2011-0016137 (2011.02.17.) Republic of Korea Registered Patent No. 10-1379649 (2014.03.24.)

The present invention is to solve the above problems, and an object of the present invention is to provide a composition for cleaning a photoresist mixture having excellent removability of a mixture of re-precipitated photoresists.

The photoresist mixture cleaning solution composition of the present invention for achieving the above object is characterized by comprising a compound represented by the following formula (1) and a compound represented by the following formula (2).

[Formula 1]

(In the formula 1,

R ₁ to R ₃ are each independently hydrogen, a hydroxy group, a C1 to C3 alkyl group, or a C1 to C3 alkoxyalkyl group,

R ₄ is a C1 to C4 linear or branched alkyl group).

[Formula 2]

(In the formula 2,

R ₅ is a C1 to C4 alkyl group).

The photoresist mixture cleaning solution composition of the present invention can more effectively remove the photoresist mixture reprecipitated in the drain by mixing with various components of the solvent in a short period of time, and maintains excellent cleaning power even after a long time. There is an advantage that corrosion does not occur.

In the present invention, when a part “includes” a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise specified.

Hereinafter, the present invention will be described in more detail.

Photoresist mixture cleaning solution composition according to an aspect of the present invention comprises a compound represented by the following formula (1) and a compound represented by the following formula (2), without corrosion in the piping in the drain, the photo reprecipitated in the drain The resist mixture can be effectively removed using a smaller amount of the cleaning liquid composition, and there is an advantage in that excellent cleaning power is maintained even after a long time.

[Formula 1]

(In the formula 1,

R ₁ to R ₃ are each independently hydrogen, a hydroxy group, a C1 to C3 alkyl group, or a C1 to C3 alkoxyalkyl group,

R ₄ is a C1 to C4 linear or branched alkyl group).

[Formula 2]

(In the formula 2,

R ₅ is a C1 to C4 alkyl group).

The'reprecipitation' will be described in detail. In the process of applying the photoresist, the residue of the photoresist remains in the nozzle, which is a passage through which the photoresist is repeatedly moved. It may be clogged, or the residue may fall off and cause a defect in the coating film. Accordingly, various solvents are used according to the type of residues deposited on each nozzle to remove the residues in the nozzles, and each of the residues dissolved in these solvents flows along the piping in the drain to move to the treatment site. At this time, the respective residues are not drained using the respective drains, but various kinds of solvents and residues pass through one drain for convenience in the process. In this way, when various types of solvents and their residues pass through a pipe in one drain, the well-dissolved residues in each solvent meet another solvents and residues to form a photoresist mixture. The mixture'reprecipitates' in the piping. When the mixtures are reprecipitated in the piping as described above, the piping may be blocked in severe cases, and when the piping is blocked, a phenomenon in which solvents and residues flow backward may cause process problems. Accordingly, the present invention provides a photoresist mixture cleaning liquid composition capable of more effectively removing the reprecipitated photoresist mixture in a smaller amount by taking the above-described configuration.

The compound represented by Chemical Formula 1 is specifically methyl propionate, ethyl propionate, propyl propionate, isobutyl propionate, butyl propionate, methyl-3-methoxypropionate, methyl-2 -Hydroxyl-2-methylpropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and the like. These may be used alone or in combination of two or more. .

According to one embodiment of the present invention, the compound represented by Chemical Formula 1 is ethyl-3-ethoxy propionate, methyl-3-methoxy propionate and methyl-2-hydroxy-2-methylpropionate Including one or more from the group consisting of may be preferable because the cleaning power for the photoresist mixture can be further improved.

According to an embodiment of the present invention, the compound represented by Chemical Formula 1 may be included in an amount of 20 to 80% by weight, preferably 25 to 75% by weight, based on 100% by weight of the total photoresist mixture cleaning solution composition comprising the same. It may be included, more preferably 30 to 70% by weight may be included. When the content of the compound represented by Chemical Formula 1 is included within the above range, there is an advantage that the cleaning power of the photoresist mixture can be improved. In particular, when the most preferable content range is satisfied, the cleaning power for the mixture may be further improved. have.

The compound represented by Chemical Formula 2 is specifically, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-sec-butyl-2-pyrrolidone, etc. Can be heard.

According to an embodiment of the present invention, the compound represented by Formula 2 is one selected from the group consisting of N-methylpyrrolidone, 1-ethyl-2-pyrrolidone and 1-butyl-2-pyrrolidone It may include the above. When two or more types of compounds represented by Chemical Formula 2 are included, the cleaning power may be improved.

According to one embodiment of the present invention, the compound represented by Chemical Formula 2 is 20 to 80% by weight, preferably 25 to 75% by weight, more preferably, based on 100% by weight of the total composition of the photoresist mixture containing the same. It may be included in 30 to 70% by weight. When the content of the compound represented by Chemical Formula 2 is included within the above range, there is an advantage that the cleaning power of the photoresist mixture can be improved. In particular, when the most preferable content range is satisfied, the cleaning power for the mixture may be further improved. have.

The cleaning liquid composition of the present invention may substantially not further include a separate water or protic solvent in that the cleaning ability for the photoresist mixture can be further improved. At this time,'substantially does not further contain a separate water or protic solvent' means that there is no water or proton solvent artificially added to the composition other than the configuration suggested in the present invention.

The protic solvent is, for example, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol Ether-based compounds such as monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; Alcohol-based compounds such as propanol, butanol, isopropanol, tetrahydrofurfuryl alcohol, ethylene glycol, and propylene glycol, and the like, but are not limited thereto.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical thought scope of the present invention. It is also natural that such modifications and modifications fall within the scope of the appended claims. In the following examples and comparative examples, "%" and "part" indicating the content are on a weight basis unless otherwise specified.

Example And Comparative example : Preparation of cleaning liquid composition

A cleaning solution composition was prepared by mixing according to the composition and contents shown in Table 1 below.

Solvent 1 weight% Solvent 2 weight% Solvent 3 weight% Example 1 EEP 30 NEP 70 - - Example 2 EEP 50 NEP 50 - - Example 3 EEP 70 NEP 30 - - Example 4 MMP 30 NMP 70 - - Example 5 MMP 50 NMP 50 - - Example 6 MMP 70 NMP 30 - - Example 7 HBM 50 NMP 50 - - Example 8 EEP 20 NMP 50 MMP 30 Example 9 EEP 30 NMP 40 MMP 30 Example 10 MMP 25 NMP 75 - - Example 11 MMP 75 NMP 25 - - Comparative Example 1 EEP 100 - - - - Comparative Example 2 NMP 100 - - - - Comparative Example 3 PGMEA 100 - - - - Comparative Example 4 PGME 100 - - - - Comparative Example 5 PGME 50 NMP 50 - - Comparative Example 6 PGME 30 EEP 70 - - Comparative Example 7 PGMEA 50 NMP 50 - - Comparative Example 8 PGMEA 30 EEP 70 - - Comparative Example 9 water 50 NMP 50 - - Comparative Example 10 water 50 EEP 50 - - Comparative Example 11 PGMEA 40 PGME 30 EEP 30 Comparative Example 12 PGMEA 40 PGME 30 NMP 30 Comparative Example 13 TMAH 10 NMP 90 - - Comparative Example 14 MEA 10 NMP 90 - - EEP: Ethyl-3-ethoxy propionate
MMP: methyl-3-methoxy propionate
HBM: methyl-2-hydroxy-2-methylpropionate
PGME: Propylene glycol monomethyl ether
PGMEA: Propylene glycol monomethyl ether acetate
NMP: N-methylpyrrolidone
NEP: 1-ethyl-2-pyrrolidone
TMAH: tetramethylammonium hydroxide
MEA: monoethanolamine

Experimental Example One. Photoresist Solubility evaluation

A specimen is prepared by curing a photosensitive resin composition composed of an organic base compound and a solvent as a methacrylate resin, a photoacid generator, and a quencher using a method known in the art, and a weight of 1:9 (photosensitive resin) Composition: by mixing the ratios of the detergent compositions of Examples and Comparative Examples) respectively, it was visually observed whether sediment was generated over time (Day 1/Day 14), and the results were evaluated according to the following evaluation criteria, Table 2 shows the results.

<Evaluation criteria>

◎: No sediment and turbidity change

○: sediment particles are not visible to the naked eye, but there is a change in turbidity

△: Sediment particles were visually confirmed.

×: gelation occurred

Experimental Example 2. Reprecipitated Photoresist Evaluation of cleaning power for the mixture

When the cleaning solution composition of Comparative Example 4 on Day 14 in Experimental Example 1 was used, 4 ml of the precipitation solution generated after a lapse of time was taken, and 0.1 g of each cleaning solution composition of the Examples and Comparative Examples was added to the precipitation solution at a time. .

At this time, the amount of the cleaning solution composition was added until all the precipitates in the precipitation solution were dissolved, and the results are shown in Table 2 below.

Day 1 Day 14 Amount of detergent required to re-dissolve the precipitate (g) Example 1 ◎ ◎ 0.2 Example 2 ◎ ◎ 0.2 Example 3 ◎ ◎ 0.2 Example 4 ◎ ◎ 0.1 Example 5 ◎ ◎ 0.1 Example 6 ◎ ◎ 0.1 Example 7 ◎ ◎ 0.2 Example 8 ◎ ◎ 0.1 Example 9 ◎ ◎ 0.1 Example 10 ◎ ◎ 0.3 Example 11 ◎ ◎ 0.4 Comparative Example 1 ◎ ◎ 0.9 Comparative Example 2 ◎ ◎ 0.6 Comparative Example 3 ◎ ◎ 1.0 Comparative Example 4 ◎ △ 2.0 or higher Comparative Example 5 ◎ ○ 1.4 Comparative Example 6 ◎ △ 2.0 or higher Comparative Example 7 ◎ ◎ 1.0 Comparative Example 8 ◎ ◎ 1.1 Comparative Example 9 △ △ 2.0 or higher Comparative Example 10 △ △ 2.0 or higher Comparative Example 11 ◎ ○ 1.5 Comparative Example 12 ◎ ○ 2.0 or higher Comparative Example 13 × × No evaluation due to precipitation Comparative Example 14 △ △ 2.0 or higher

Referring to Table 2 above, when all the configurations of the present invention are included (Examples 1 to 11), the cleaning power for the photoresist is excellent, as well as the configuration of the present invention is not included after 14 days. When compared with the case (Comparative Examples 1 to 14), it was confirmed that the solubility in the photoresist remains excellent.

In addition, it was confirmed that it is possible to dissolve the precipitated photoresist mixture even with a smaller amount of the cleaning liquid composition than Comparative Examples 1 to 12, which does not contain any one of the components of the present invention, that is, it has been confirmed that the cleaning power is excellent. In the case of Comparative Examples 13 and 14, it was confirmed that sediment was generated and a problem in that solubility was remarkably lowered was generated.

Claims (7)

A photoresist mixture cleaning solution composition comprising a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2:
[Formula 1]

(In the formula 1,
R ₁ to R ₃ are each independently hydrogen, a hydroxy group, a C1 to C3 alkyl group, or a C1 to C3 alkoxyalkyl group,
R ₄ is a C1 to C4 linear or branched alkyl group).
[Formula 2]

(In the formula 2,
R ₅ is a C1 to C4 alkyl group). According to claim 1,
The compound represented by Chemical Formula 1 may include at least one selected from the group consisting of ethyl-3-ethoxy propionate, methyl-3-methoxy propionate and methyl-2-hydroxy-2-methylpropionate. Photoresist mixture cleaning liquid composition comprising a. According to claim 1,
The compound represented by Chemical Formula 2 is a photoresist mixture cleaning solution composition comprising at least one selected from the group consisting of N-methylpyrrolidone, N-ethylpyrrolidone and N-butylpyrrolidone. According to claim 1,
The compound represented by the formula (1) is a photoresist mixture cleaning liquid composition, characterized in that contained in 20 to 80% by weight relative to 100% by weight of the total composition containing it. According to claim 4,
The compound represented by Formula 1 is a photoresist mixture cleaning liquid composition, characterized in that contained in 30 to 70% by weight relative to 100% by weight of the total composition containing it. According to claim 1,
The compound represented by the formula (2) is a photoresist mixture cleaning liquid composition, characterized in that contained in 20 to 80% by weight relative to the total 100% by weight of the composition containing it. The method of claim 6,
The compound represented by the formula (2) is a photoresist mixture cleaning liquid composition, characterized in that contained in 30 to 70% by weight relative to 100% by weight of the total composition containing it.